Process for the production of condensation products



Patented June 27,

UNITED :STATES PATENT OFFICE PROCESS FOR THE PRODUCTION OF CONDENSATIONPRODUCTS Heinrich Hopfl, August Weickmann, and Rudolf Kern,Ludwigshalen-on-the-Rhine, Germany,

assignors to General Aniline & Film (lorporation, New York, N. 2., acorporation of Delaware No Drawin A lion June 1, 1940', Serial No.

2 P 338,374. Germany June 7, i939 12, Claims.

The present invention relates to a process for the production ofcondensation products.

We hove found thot condensation products which are useful for quite a.variety of applications are obtained by causing carbonyl come pounds, i.e. aldehydes and/or ketones, to not upon aliphatic dismines containingmore than 5 carbon atoms in the molecule.

The products which are no longer crystalline but have not yet beencondensed to completion are soluble in ketones, alcohols and others andare suitable for lncquering purposes.

Diomines suitable for the reaction are, for ex- By the reaction,depending on the working.

conditions applied and the diamines and olde=- hydes or hetones used,condensation products of a varying degree of condensation are obtained.The products of a, relatively low degree of corn densation arecrystalline. They are suitable for example as plasticizers for the veryhighly condensed products; they may be further condensed, to formproducts of a higher degree of condensation. They pass various stages ofcondensation similar to heat-hardenable resins, such as phenolsldehyderesins. In passing through the-difierent stages oi condensation they aretransformed first into soluble and iusible products which are no longercrystalline or distillable, whereupon, on further condensation, forexample under the influence 0! heat and pressure, they are con vertedinto insoluble products and thus arrive at the final stage of thecondensation. The condensation products obtained are considerably moreelastic than the usual phenol resins.

The condensation may be carriedout by merely mixing the initialmaterials or by heating them to elevated temperatures, if desired insolution. Usually temperatures below 100 C. are employed The reactionproceeds with a considerable evolution of heat. The water formed in thecondensation may be removed by means oi water-binding agents or byazeotropic distillation. In advanced stages of the condensation thewater which then separates from the reaction mixture, may be removedmechanically, the remaining parts being then distilled off during thefurther condensation.

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The more highly condensed products are suitable for use in theproduction of shaped articles, especially by molding, pressing orinjectionmolding.

The following examples serve to illustrate how the said invention may becarried out in practice, but the invention is not restricted to the saidexamples. The parts'are by weight.

limompie 1 A solution of no parts of hexametliylene diemine in 5% partsof methanol is run into an alcoholic solution of 134 ports-o!terephthalic aldehyde within half an hour, while stirring. After itshort time the primary reaction product sepsrates in the form ofbeautiful colorless crystals melting at 178 C. The crystals are filteredoh by suction and further condensed by heating. if desired in vacuo, toform a clear colorless resin. The condensation may be discontinued atany point where it meets the demands 01' a certain application; forexample ii films, bands end'like articles are aimed at, the condensationmay be stopped when the product is viscous in the heat; it moldingpowders are desired the product is further condensed until it is fusibleonly by the application or pressure.

' Example 2 280 parts of crotonaldehyde are added to 232 Example 3 1molecular proportion 01' hexamethylene diamine is mixed with 2 molecularproportions or more or vinyl methyl ketone: the temperature 0! themixture rises so strongly that the mixture is brought to boiling. Thereaction product may be further condensed or polymerized by heating, ifdesired in the presence or a peroxide.

Example 4 155 parts 01 crotonaldehyde are slowly run into- 204 parts ofw.o'-diamino-dipropyl ether of butanediol-L4 (H2NC3HeO--C4Ha-OC:Hs-NH:)

while well stirring. The temperature of the mass rises spontaneously andshortly after the reac-.

tion water begins to separate; after completion oi. the reaction thewater is removed by distillation in vacuo. A very flexible resin is thusobtained which in its first stage of condensation is soluble in lacquersolvents, as for example acetic ester. The films obtained by causing thesolvent to evaporate may be hardened by drying in the air or by heating.

What we claim is:

1. The process of producing condensation products which consists ofcondensing a primary aliphatic diamine containing at least 6 carbonatoms and only two amino groups with a monomeric carbonyl compoundselected from the class consisting of aldehydes and ketones in themolecular ratio of about one carbonyl group of the carbonyl compoundsfor each amino group of the diamine;

2. The process of producing condensation products which consists ofcondensing a, primary aliphatic diamine containing at least 6 carbonatoms and only two amino groups with a monomeric carbonyl compoundselected from the class consisting of aldehydes and ketones in themolecular ratio or about one carbonyl group or the carbonyl compoundsfor each amino group of the diamine at a temperature below 100 C.

3. The process of producing condensation products which consists ofcondensing hexamethylene diamine with a monomeric carbonyl compoundselected from the class consisting of aldehydes and ketones in themolecular ratio of about one carbonyl group of the carbonyl compoundsfor each amino group or the diamine.

4. The process of producing condensation products which consists ofcondensing hexamethylene diamine with a monomeric carbonyl compoundcarbonyl group of the carbonyl compounds for each amino group of thediamine at a temperature below 100 C.

5. Condensation products which consist ota primary aliphatic diaminecontaining at least 8 carbon atoms and only two amino groups withmonomeric carbonyl compounds selected from the class consisting ofaldehydes and ketones in the molecular ratio of about one carbonyl groupof the carbonyl compounds for each amino group of the diamine.

6. Condensation products which consist of hexamethylene diamine withmonomeric carbonyl 8. The process of producing condensation prod- I uctswhich consists of condensing one molecular proportion 01' hexamethylenediamine with two molecular proportions of crotonaldehyde.

9. The process of producing condensation products which consists ofcondensing one molecular proportion of hexamethylene diamine with twoselected from the class consisting or aldehydes and ketones in themolecular ratio oiabout one molecular proportions of vinyl methylketone.

10. A product which consists of the condensation product obtained bycondensing one molecular proportion of hexamethylene diamine with onemolecular proportion of terephthalic aide-- hyde.

11. A product which consists of the condensation product obtained bycondensing one molecular proportion of hexamethylene diamine with twomolecular proportions of crotonaldehyde.

12. A product which consists of the condensation product obtained bycondensing one molecular proportion of hexamethylene diamine with twomolecular proportions of vinyl methyl ketone.

HEINRICH HOPFP'. 1 AUGUST WEICKMANN. RUDOLF KERN.

